Titanium Imido Complexes by Displacement of –SiMe₃ and C–H Bond Activation in a Ti^III Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC)

A strong σ‐donating cyclic (alkyl)(amino) carbene (cAAC) triggers rearrangement of the silyl(aryl) amido ligand –N(SiMe 3 )Dipp (Dipp = 2,6‐diisopropylphenyl) in the coordination sphere of titanium(III) to afford a novel zwitterionic titanium imido complex with a TiCH 2 SiMe 2 [cAAC] linkage. Reduction of this species produces a new DippN=Ti imido complex containing a cAAC‐centered radical species, characterized by single‐crystal diffraction analysis and electron paramagnetic resonance spectroscopy.